Hair dye composition

ABSTRACT

The invention relates to a hair dye composition having markedly high dyeing power, less color fade over time, and undergoes a small change in the color tone of the dye even after storage.

TECHNICAL FIELD

The present invention relates to a hair dye composition having markedlyhigh dyeing power, can strongly impart the hair with an extremely vividcolor ranging from yellow, red, blue to green, has less color fade overtime and undergoes a small change in the color tone of the dye evenafter storage.

BACKGROUND ART

Hair dyes can be classified by the dye to be used therefor, or whetherthey have bleaching action of melanin or not. Typical examples include atwo-part permanent hair dye composed of a first part containing analkali agent, an oxidation dye and a direct dye such as nitro dye and asecond part containing an oxidizing agent; and one-part semi-permanenthair dye containing an organic acid or an alkali agent, and a direct dyesuch as acid dye, basic dye or nitro dye.

The above-described permanent hair dye is however accompanied with thedrawbacks that color tone imparted by an oxidation dye is not so vividand the color of the hair dyed with a vivid-color producing nitro dyeordinarily employed as a direct dye markedly fades over time and becomesdull soon even if the color tone rightly after dyeing is very vivid(Japanese Patent Application Laid-Open (Kokai) No. Hei 6-271435).

Recently, hair dyes containing as a direct dye a so-called cationic dyehaving a cation group contained in their conjugate system have beenreported (Japanese Language Laid-Open Publication (PCT) No. Hei8-507545, 8-501322 or 10-502946, or Japanese Patent ApplicationLaid-Open (Kokai) No. Hei 10-194942). They have been found to involvedrawbacks that intended dyeing effects are not available owing todecomposition of them caused by mixing, upon hair dyeing, with hydrogenperoxide ordinarily employed as an oxidizing agent; and that when acation group is contained in an azo-based (—N═N—) conjugated system,they are unstable to an alkali agent or a reducing agent essentiallycontained in a permanent hair dye.

DISCLOSURE OF THE INVENTION

An object of the present invention is to provide a hair dye compositionwhich has high hair dyeing power, less color fade over time, andexcellent storage stability to permit only a small change in color toneof the dye after storage.

The present inventors have found that when the below-described compoundsknown as photosensitizing dye or sensitizing dye [Journal of SyntheticOrganic Chemistry, Japan, 32(12), 971-988 (1974), etc.] are used as ahair dye, the resulting dye composition can strongly impart the hairwith a vivid color ranging from yellow, red, blue to green withoutdecomposing the dye upon hair drying, exhibits excellent lightresistance, washing resistance, perspiration resistance, frictionresistance and heat resistance, and undergoes a small change in thecolor tone of the dye after storage as compared with that rightly afterpreparation because the dye exists in the composition stably.

In one aspect of the present invention, there is thus provided a hairdye composition comprising, as a direct dye, a compound represented bythe following formula (I), (II), (III) or (IV):

wherein, m stands for 0, 1 or 2, n stands for 1 or 2,

m units of R¹ and n units of R⁴ each independently represents a hydrogenatom, a C₁₋₄ alkyl group or a halogen atom, m units of R² eachindependently represents a hydrogen atom, a C₁₋₄ alkyl group or an arylgroup, with the proviso that at m=2, two R²s, taken together with theadjacent ═C—CH═C—, may form a carbocyclic structure or anoxygen-containing heterocyclic structure, n units of R³ eachindependently represents a hydrogen atom or a C₁₋₄ alkyl group, n unitsof R⁵ each independently represents a hydrogen atom or a C₁₋₄ alkylgroup, or is bonded, via a group —CO—O—, to a ring B⁵ to form a lactonering, R⁶ represents a hydrogen atom or a C₁₋₄ alkyl group,

A¹ represents the below-described formula (1), (2) or (3), A² representsthe below-described formula (4), A³ represents the below-describedformula (5), (6), (7), (8) or (9), A⁴ and Z¹ each independentlyrepresents the below-described formula (10), (11), (12), (13), (14),(15) or (16), Z² represents the below-described formula (17), Z³represents the below-described formula (18), (19), (20) or (21):

 (in which, a broken line means presence or absence of π bonding, D¹represents an oxygen atom, a sulfur atom or a group NR²⁵, D² representsan oxygen atom, a sulfur atom, a group NR²⁶ or a group CR²⁷R²⁸, D³represents a nitrogen atom or a group CR²⁹, D⁴ represents an oxygenatom, a sulfur atom or a group NR³⁰, R⁷, R⁸, R⁹, R¹⁴ and R²⁵ eachindependently represents a C₁₋₆ alkyl group which may have asubstituent, R¹⁰, R¹¹, R¹³, R¹⁵, R¹⁶, R²¹, R²², R²⁷, R²⁸ and R²⁹ eachindependently represents a hydrogen atom or a C₁₋₆ alkyl group, R¹² andR²⁶ each independently represents a hydrogen atom or a C₁₋₆ alkyl groupwhich may have a substituent, R¹⁷ and R¹⁸ each independently representsa hydrogen atom, a C₁₋₆ alkyl group which may have a substituent or anaryl group which may have a substituent, or R¹⁷ and R¹⁸, taken togetherwith the adjacent nitrogen atom, form a nitrogen-containing heterocycleor one or both of R¹⁷ and R¹⁸ is (are) bonded to the ring B⁵ to form anitrogen-containing heterocycle, R¹⁹ and R²³ each independentlyrepresents an aryl group which may have a substituent, R²⁰ represents aC₁₋₆ alkyl group, R²⁴ and R³⁰ each independently represents a hydrogenatom, a C₁₋₆ alkyl group which may have a substituent, or an aryl groupwhich may have a substituent, Y¹ and Y² each independently represents anoxygen atom or a sulfur atom, rings B¹, B², B³ and B⁴ each independentlyhas a ring structure which may have, as a substituent, a halogen atom,an aryl group or a C₁₋₄ alkyl group or may further be cyclocondensedwith a benzene ring, B⁵ has a ring structure which may have, as asubstituent, a halogen atom, an aryl group or a C₁₋₄ alkyl group, may becondensed with a benzene ring, or may be bonded to R¹⁷ or R¹⁸ to have aring structure which may be cyclocondensed with a nitrogen-containingheterocycle), and

X⁻ represents an anion, with the proviso that X⁻ does not exist when R⁷,R⁸, R⁹ and R²⁵ each has a sulfonium group as a substituent.

In another aspect of the present invention, there is also provided amethod for dyeing the hair with the above-described hair dyecomposition.

BEST MODE FOR CARRYING OUT THE INVENTION

In the formulas (I) to (IV), m is preferably 0 or 1 and n is preferably1 from the viewpoint of stability in the hair dye composition.

Examples of the C₁₋₄ alkyl group represented by R¹ or R⁴ include methyl,ethyl and butyl groups, those of the halogen atom include chlorine,bromine and fluorine atoms. As each of R¹ and R⁴, a hydrogen atom ismost preferred.

Examples of the C₁₋₄ alkyl group represented by R² include methyl, ethyland butyl groups, those of the aryl group include phenyl group. Examplesof the carbocyclic structure which may be formed at m=2 by two R²s whenthey are taken together with the adjacent ═C—CH═C— include cyclohexenering and cyclopentene ring. As the oxygen-containing heterocyclicstructure, 4H-pyrane ring can be mentioned as an example. These ringsmay be substituted by an alkyl group. As R², hydrogen atom and C₁₋₄alkyl groups are preferred, of which the hydrogen atom, methyl group andethyl group are particularly preferred.

Examples of the C₁₋₄ alkyl group represented by R³ or R⁶ include methyl,ethyl and butyl groups. As each of R³ and R⁶, hydrogen atom is mostpreferred.

Examples of the C₁₋₄ alkyl group represented by R⁵ include methyl, ethyland butyl groups, while those of the lactone ring which may be formed bybonding of R⁵ to the ring B⁵ via —CO—O— include coumalin ring (includingring B⁵). As R⁵, hydrogen atom is most preferred.

As examples of the substituents for the groups (1) to (21) representedby each of A¹ to A⁴ and Z¹ to Z³, the below-described ones can bementioned.

Examples of the C₁₋₆ alkyl group represented by R⁷, R⁸, R⁹, R¹², R¹⁴,R²⁵ or R²⁶ include methyl, ethyl, propyl, isopropyl and cyclohexylgroups, which may each be substituted by an aryl (such as phenyl),sulfonium, carboxy or vinyl group. Particularly preferred examples ofR⁷, R⁸, R⁹, R¹⁴ or R²⁵ include methyl and ethyl groups, while those ofR¹² and R²⁶ include hydrogen atom, methyl group and ethyl group.

Examples of the C₁₋₆ alkyl group represented by R¹⁰, R¹¹, R¹³, R¹⁵, R¹⁶,R²⁰, R²¹, R²², R²⁷, R²⁸ or R²⁹ include methyl, ethyl, butyl and hexylgroups. Particularly preferred examples of R¹⁰, R¹¹, R¹³, R¹⁵, R¹⁶ andR²⁹ include hydrogen atom, those of R²⁰, R²⁷ or R²⁸ include methylgroup, and those of R²¹ or R²² include hydrogen atom and methyl group.

Examples of the C₁₋₆ alkyl group represented by R¹⁷ or R¹⁸ includemethyl, ethyl, propyl, butyl, hexyl, isopropyl and cyclohexyl groups,which may each be substituted by an aryl group (such as phenyl), cyanogroup or halogen atom (such as chlorine atom). Examples of the arylgroup represented by R¹⁷ or R¹⁸ include phenyl and naphthyl groups,which may each be substituted by an amino group. Examples of the ringwhich may be formed by R¹⁷ and R¹⁸ when they are taken together with theadjacent nitrogen atom include pyrrolidine, piperidine, morpholine andpiperazine rings. Examples of the nitrogen-containing heterocycle whichmay be formed by bonding of either one or both of R¹⁷ and R¹⁸ to thering B⁵ include julolidine ring (including ring B⁵). Particularlypreferred examples of R¹⁷ or R¹⁸ include hydrogen atom, methyl group andethyl group.

Examples of the aryl group represented by R¹⁹ or R²³ include phenyl andnaphthyl groups, which may each be substituted by a sulfonium group. Aseach of R¹⁹ and R²³, unsubstituted phenyl group is most preferred.

Examples of the C₁₋₆ alkyl group represented by R²⁴ or R³⁰ includemethyl, ethyl, propyl, butyl, hexyl, isopropyl and cyclohexyl groups,which may each be substituted by an aryl (such as phenyl), carboxy orvinyl group. Examples of the aryl group represented by R²⁴ or R³⁰include phenyl and naphthyl groups, which may each be substituted by asulfonium group. Particularly preferred as each of R²⁴ and R³⁰ arehydrogen atom, methyl group and ethyl group.

As each of Y¹ and Y², an oxygen atom is more preferred.

As a substituent for each of the rings B¹ to B⁵, examples of the halogenatom include chlorine, bromine and fluorine atoms, those of the arylgroup include phenyl group, and those of the C₁₋₄ alkyl group includemethyl, ethyl and butyl. As each of the rings B¹ to B⁵, an unsubstitutedone is preferred. These rings may each be cyclocondensed with a benzenering. The ring cyclocondensed with a benzene ring is preferred as wellas the above-described uncyclocondensed ring.

Examples of the anion represented by X⁻ in the formula (I) or (II)include chloride ions, bromide ions, iodide ions, trichlorozincic acidions, tetrachlorozincic acid ions, sulfuric acid ions, hydrosulfuricacid ions, methyl sulfate ions, phosphoric acid ions, formic acid ionsand acetic acid ions. When a group (R⁷, R⁸, R⁹ or R²⁵) to be bonded to anitrogen atom has a sulfonium group as a substituent, X⁻ does not existbecause a counterion is formed in the molecule.

In Compounds (I) to (IV), as A¹, preferred are the groups (1)(particularly, D¹=O, NR²⁵) and (2); as A³, preferred are the groups (5)(particularly, D²=O, NR²⁶, CR²⁷R²⁸), (6) and (8); as A⁴, preferred arethe groups (10) (particularly, D²=O, NR²⁶, CR²⁷R²⁸), (11), (12), (14)and (15); as Z¹, particularly preferred are the group (10) (D²=O) whenA¹ is the group (1) (D¹=O), the group (10) (D²=NR²⁶) when A¹ is a group(1) (D¹=NR²⁵), the group (11) when A¹ is the group (2) (at 2-position),the group (12) when A¹ is a group (2) (at 4-position); and as Z³,preferred are the groups (18), (19) and (21) (particularly, D⁴=NR³⁰).Out of Compounds (I) to (IV), Compounds (I) to (III), particularlyCompound (I) is preferred.

Specific examples of the direct dyes (I) to (IV) to be used in thepresent invention will next be shown.

As a direct dye, at least one of these direct dyes (I) to (IV) can beused. It is also possible to use another direct dye in combinationtherewith. In particular, when the direct dye (I), (II), (III) or (IV)is a yellow dye, combination with red and blue dyes, when it is a reddye, combination with yellow and blue dyes, and when it is a blue dye,combination with yellow and red dyes, each makes it possible to dye thehair with a deep and highly lustrous dark brown or black color.

Examples of the direct dye other than the direct dyes (I) to (IV)include Basic Blue 7 (C.I. 42595), Basic Blue 26 (C.I. 44045), BasicBlue 99 (C.I. 56059), Basic Violet 10 (C.I. 45170), Basic Violet 14(C.I. 42515), Basic Brown 16 (C.I. 12250), Basic Brown 17 (C.I. 12251),Basic Red 2 (C.I. 50240), Basic Red 22 (C.I. 11055), Basic Red 76 (C.I.12245), Basic Red 118 (C.I. 12251:1) and Basic Yellow 57 (C.I. 12719);and basic dyes as described in Japanese Patent Publication No. Sho58-2204, Japanese Patent Application Laid-Open (Kokai) No. Hei 9-118832,Japanese Language Laid-Open Publication (PCT) No. Hei 8-501322 orJapanese Language Laid-Open Publication (PCT) No. Hei 8-507545.

The direct dyes (I) to (IV) are each preferably added in an amount of0.01 to 20 wt. %, more preferably 0.05 to 10 wt. %, especially 0.1 to 5wt. % based on the whole composition (after mixture of all the componentparts when the hair dye composition is a two part or three part type;this will apply equally hereinafter). When another direct dye is addedin combination, the content of it in total with the direct dye (I),(II), (III) or (IV) preferably ranges from 0.05 to 10 wt. %, especially0.1 to 5 wt. %.

The hair dye composition of the present invention is preferably adjustedto pH 6 to 11, with pH 8 to 11 being especially preferred. Examples ofthe alkali agent to be used for pH adjustment include ordinarilyemployed ones such as ammonia, organic amines and salts thereof. Thealkali agent is preferably added in an amount of 0.01 to 20 wt. %, morepreferably 0.1 to 10 wt. %, especially 0.5 to 5 wt. % based on the wholecomposition.

In the hair dye composition of the present invention, an oxidizing agentcan be incorporated. In this case, hair dyeing and bleaching can becarried out simultaneously, which facilitates more vivid hair dyeing.Ordinarily employed oxidizing agents, for example, hydrogen peroxide,persulfates such as ammonium persulfate, potassium persulfate and sodiumpersulfate, perborates such as sodium perborate, percarbonates such assodium percarbonate and bromates such as sodium bromate and potassiumbromate are usable. Out of them, hydrogen peroxide is especiallypreferred. The oxidizing agent is added in an amount of 0.5 to 10 wt. %,especially 1 to 8 wt. %, based on the whole composition.

In the hair dye composition of the present invention, an oxidation dyecan be incorporated further. This incorporation enables markedly vividdyeing not attainable by the single use of an oxidation dye. In thiscase, the above-exemplified oxidizing agents can be used as an oxidizingagent, with hydrogen peroxide being particularly preferred.Alternatively, an oxidizing enzyme such as laccase can be employed. Forthe oxidation dye, known color developers and couplers ordinarilyemployed for an oxidation type hair dye can be used.

Examples of the developer include p-phenylenediamines having one orseveral groups selected from groups NH₂—, NHR— and NR₂— (in which Rrepresents a C₁₋₄ alkyl or hydroxyalkyl group) such asp-phenylenediamine, p-toluylenediamine, N-methyl-p-phenylenediamine,chloro-p-phenylenediamine, 2-(2′-hydroxyethylamino)-5-aminotoluene,N,N-bis-(2-hydroxyethyl)-p-phenylenediamine,2-hydroxyethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine,methoxy-p-phenylenediamine, 2,6-dichloro-p-phenylenediamine,2-chloro-6-methyl-p-phenylenediamine,6-methoxy-3-methyl-p-phenylenediamine, 2,5-diaminoanisole,N-(2-hydroxypropyl)-p-phenylenediamine andN-2-methoxyethyl-p-phenylenediamine; 2,5-diaminopyridine derivatives and4,5-diaminopyrazole derivatives; p-aminophenols such as p-aminophenol,2-methyl-4-aminophenol, N-methyl-p-aminophenol, 3-methyl-4-aminophenol,2,6-dimethyl-4-aminophenol, 3,5-dimethyl-4-aminophenol,2,3-dimethyl-4-aminophenol and 2,5-dimethyl-4-aminophenol;o-aminophenols, o-phenylenediamines, 4,4′-diaminophenylamine andhydroxypropylbis(N-hydroxyethyl-p-phenylenediamine); and salts thereof.

Examples of the coupler include 1-naphthol, 1,5-dihydroxynaphthalene,1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene,5-amino-2-methylphenol, 5-(2′-hydroxyethylamino)-2-methylphenol,2,4-diaminoanisole, m-toluylenediamine, resorcin, m-phenylenediamine,m-aminophenol, 4-chlororesorcin, 2-methylresorcin,2,4-diaminophenoxyethanol, 2,6-diaminopyridine,2-amino-3-hydroxypyridine, 4-hydroxyindole, 6-hydroxyindole,2,4-diamino-6=hydroxypyrimidine, 2,4,6-triaminopyrimidine,2-amino-4,6-dihydroxypyrimidine, 4-amino-2,6-dihydroxypyrimidine,4,6-diamino-2-hydroxypyrimidine and 1,3-bis(2,4-diaminophenoxy)propane;and salts thereof.

As each of a developer and a coupler, at least one of theabove-exemplified ones can be used. Although no particular limitation isimposed on the content of each of them, it is added in an amount of 0.01to 20 wt. %, especially 0.5 to 10 wt. % based on the whole composition.

To the hair dye composition of the present invention, a knownautoxidation dye typified by an indole or an indoline, or a known directdye such as a nitro dye or a disperse dye can also be added.

When an anionic component (such as anionic surfactant or anionicpolymer) is added to the hair dye composition of the present inventionin the case where the direct dye (I) or (II) to be incorporated in thecomposition is a cationic dye, it is preferred to satisfy the followingequation:

“Ion activity concentration of the anionic component/ion activityconcentration of the cationic direct dye (I) or (II) incorporated in thehair dye composition≦8”

The term “ion activity concentration” as used herein means “molarconcentration×ionic valence”.

Addition of a polyol, polyol alkyl ether, cationic or amphoteric polymeror silicone to the hair dye composition of the present invention ispreferred, because the resulting composition can dye the hair uniformlyand improve the cosmetic effects of the hair.

In addition to the above-described components, those ordinarily employedas a raw material for cosmetics can be added to the hair dye compositionof the present invention. Examples of such an optional component includehydrocarbons, animal or vegetable fats and oils, higher fatty acids,organic solvents, penetration promoters, cationic surfactants, naturalor synthetic polymers, higher alcohols, ethers, amphoteric surfactants,nonionic surfactants, protein derivatives, amino acids, antiseptics,chelating agents, stabilizing agents, antioxidants, plant extracts,crude drug extracts, vitamins, colorants, perfumes and ultravioletabsorbers.

The hair dye composition of the present invention can be prepared in aconventional manner into a one-part composition, a two-part compositionhaving a first component part containing an alkali agent and a secondcomponent part containing an oxidizing agent, or a three-partcomposition having, in addition to these two component parts, a powderyoxidizing agent such as persulfate. The direct dye (I), (II), (III) or(IV) can be incorporated in either one or both of these component partsof the two-part or three-part composition. When the hair dye compositionof the present invention is one-part type, it is applied to the hairdirectly, while when it is a two- or three-part type, it is applied tothe hair after mixing these parts upon hair dyeing.

No particular limitation is imposed on the form of the hair dyecomposition of the present invention. Examples include powder,transparent liquid, emulsion, cream, gel, paste, aerosol, and aerosolfoam. It preferably has a viscosity of 2000 to 100000 mpa·s in the stageof application to the hair (after mixing of all the components when thehair dye composition is a two-part or three-part type).

EXAMPLES

Direct dyes (I) to (IV) [Compounds (a) to (g)] and another direct dyes[Compounds (i), (ii)] used in the below-described examples are asfollows:

Examples 1 to 12

In a manner known per se in the art, hair dyes as shown in Tables 1 to 3were prepared.

TABLE 1 Examples (wt. %) 1 2 3 4 5 Dye [Compound (a)] 0.2 0.15 0.1 Dye[Compound (c)] 0.5 0.1 0.2 Dye [Compound (i), Red] 0.15 0.1 0.05 Dye[Compound (ii), Yellow] 0.1 0.1 Ethanol 5 5 5 Propylene glycol 5 5Diethylene glycol monoethyl ether 10 Guar gum 1 Hydroxypropyl guar gum 11 1 1 “Gufquat 734” (trade name; product of 1 1 ISP Japan) “CatinalLC100” (trade name; product of 1 1 Toho Chemical Industry)“Polyether-modified silicone KF6005” 0.4 (trade name; product ofShin-Etsu Chemical) “Amodimethicone SM8702C” (trade 1.5 name; product ofDow Corning Toray Silicone) Monoethanolamine 0.1 Phosphoric acid Amountto adjust pH to 9 Perfume q.s. Water Balance

TABLE 2 Examples (wt. %) 6 7 8 9 1st Dye [Compound (b)] 0.2 0.15 0.2part Dye [Compound (d)] 0.1 0.15 Dye [Compound (ii), Yellow] 0.1 0.05Dye [Basic Blue 99] 0.3 28 wt. % Aqueous ammonia  5 Monoethanolamine  2Propylene glycol  8 Polyoxyethylene (20) isostearyl ether 24Polyoxyethylene (2) isostearyl ether 20 “Merquat 280” (trade name;product of 8 Calgon Corp., a 35 wt. % aqueous solution) “Polymer JR400”(trade name; product of 0.5 0.5 Union Carbide) “Amodimethicone SM8702C”(trade 2 name; product of Dow Corning Toray Silicone) “Polyethermodified silicone KF6005” 0.3 (trade name; product of Shin-EtsuChemical) Tetrasodium ethylenediaminetetraacetate  0.1 Perfume q.s.Ammonium chloride Amount to adjust pH to 10 Water Balance 2nd 35 wt. %Aqueous hydrogen peroxide 17.1 part Methylparaben  0.1 Phosphoric acidAmount to adjust pH to 3.5 Water Balance

TABLE 3 Examples (wt. %) 10 11 12 1st Toluene-2,5-diamine 1.9 1 partPara-aminophenol 1 Resorcin 2 Para-amno-orhto-cresol 1.12,4-Diaminophenoxyethanol 1.37 Dye [Compound (f)] 0.05 Dye [Compound(e)] 0.15 Dye [Compound (g)] 0.1 28 wt. % Aqueous ammonia 5Monoethanolamine 2 Propylene glycol 8 Polyoxyethylene (20) isostearylether 24 Polyoxyethylene (2) isostearyl ether 20 “Merquat 280” (tradename; product of 8 Calgon Corp., a 35 wt. % aqueous solution) “PolymerJR400” (trade name; product 0.5 of Union Carbide) “AmodimethiconeSM8702C” (trade name; 2 product of Dow Corning Toray Silicone) Sodiumsulfite 0.05 Ascorbic acid 0.5 Tetrasodium ethylenediaminetetraacetate0.1 Perfume q.s. Ammonium chloride Amount to adjust pH to 10 WaterBalance 2nd 35 wt. % Aqueous hydrogen peroxide 17.1 part Methylparaben0.1 Phosphoric acid Amount to adjust pH to 3.5 Water Balance

Example 13

In a manner known per se in the art, the below-described hair dye wasprepared.

(First part) (wt. %) Para-aminophenol 1 Para-amino-ortho-cresol 1.1Compound (d) 0.1 28 wt. % Aqueous ammonia 5 Monoethanolamine 2 Cetanol8.5 Polyoxyethylene (40) cetyl ether 3 Polyoxyethylene (2) cetyl ether3.5 Stearyl trimethyl ammonium chloride 2 Liquid paraffin 0.5 Sodiumsulfite 0.05 Ascorbic acid 0.5 Tetrasodium ethylenediaminetetraacetate0.1 Perfume q.s. Ammonium chloride Amount to adjust pH to 10 WaterBalance

(Second part) (wt. %) 35 wt. % Aqueous hydrogen peroxide 17.1Methylparaben 0.1 Phosphoric acid Amount to adjust pH to 3.5 WaterBalance

What is claimed is:
 1. A hair dye composition, comprising: a one-partaqueous formulation containing a direct dye compound represented byformula (1), (II), (III) or (IV):

wherein, m stands for 0, 1 or 2, n stands for 1 or 2, m units of R¹ andn units of R⁴ each independently represents a hydrogen atom, a C₁₋₄alkyl group or a halogen atom, m units of R² each independentlyrepresents a hydrogen atom, a C₁₋₄ alkyl group or an aryl group, withthe proviso that at m=2, two R²s, taken together with the adjacent═C—CH═C—, may form a carbocyclic structure or an oxygen-containingheterocyclic structure, n units of R³ each independently represents ahydrogen atom or a C₁₋₄ alkyl group, n units of R⁵ each independentlyrepresents a hydrogen atom or a C₁₋₄ alkyl group, or is bonded, via agroup —CO—O—, to a ring B⁵ to form a lactone ring, R⁶ represents ahydrogen atom or a C₁₋₄ alkyl group, A¹ represents the below-describedformula (1), (2) or (3), A² represents the below-described formula (4),A³ represents the below-described formula (5), (6), (7), (8) or (9), A⁴and Z¹ each independently represents the below-described formula (10),(11), (12), (13), (14), (15) or (16), Z² represents the below-describedformula (17), Z³ represents the below-described formula (18), (19), (20)or (21):

 wherein a broken line means the presence or absence of bonding, D¹represents an oxygen atom, a sulfur atom or a group NR²⁵, D² representsan oxygen atom, a sulfur atom, a group NR²⁶ or a group CR²⁷R²⁸, D³represents a nitrogen atom or a group CR²⁹, D⁴ represents an oxygenatom, a sulfur atom or a group NR³⁰, R⁷, R⁸, R⁹, R¹⁴ and R²⁵ eachindependently represents a C₁₋₆ alkyl group which may have asubstituent, R¹⁰, R¹¹, R¹³, R¹⁵, R¹⁶, R²¹, R²², R²⁷, R²⁸ and R²⁹ eachindependently represents a hydrogen atom or a C₁₋₆ alkyl group, R¹² andR²⁶ each independently represents a hydrogen atom or a C₁₋₆ alkyl groupwhich may have a substituent, R¹⁷ and R¹⁸ each independently representsa hydrogen atom, a C₁₋₆ alkyl group which may have a substituent or anaryl group which may have a substituent, or R¹⁷ and R¹⁸, taken togetherwith the adjacent nitrogen atom, form a nitrogen-containing heterocycleor one or both of R¹⁷ and R¹⁸ is (are) bonded to the ring B⁵ to form anitrogen-containing heterocycle, R¹⁹ and R²³ each independentlyrepresents an aryl group which may have a substituent, R²⁰ represents aC₁₋₆ alkyl group, R²⁴ and R³⁰ each independently represents a hydrogenatom, a C₁₋₆ alkyl group which may have a substituent, or an aryl groupwhich may have a substituent, Y¹ and Y² each independently represents anoxygen atom or a sulfur atom, rings B¹, B², B³ and B⁴ each independentlyhas a ring structure which may have, as a substituent, a halogen atom,an aryl group or a C₁₋₄ alkyl group or may further be cyclocondensedwith a benzene ring, B⁵ has a ring structure which may have, as asubstituent, a halogen atom, an aryl group or a C₁₋₄ alkyl group, may becondensed with a benzene ring, or may be bonded to R¹⁷ or R¹⁸ to have aring structure which may be cyclocondensed with a nitrogen-containingheterocycle, and X⁻ represents an anion, with the proviso that X⁻ doesnot exist when R⁷, R⁸, R⁹ and R²⁵ each has a sulfonium group as asubstituent, the composition having a pH ranging from 6-11 that isadjusted to within said range by an alkali agent and containing at leastone cosmetic ingredient selected from the group consisting ofhydrocarbons, animal or vegetable fats and oils, fatty acids, organicsolvents, hair penetration promoters, cationic surfactants, natural orsynthetic polymers, alcohols, ethers, amphoteric surfactants, nonionicsurfactants, protein derivatives, amino acids, antiseptics, chelatingagents, stabilizing agents, antioxidants, plant extracts, crude drugextracts, vitamins, colorants, perfumes, aerosolizing agents and UVabsorbers.
 2. A hair dye composition, comprising: a two-part aqueousformulation comprising, in a first part, a direct dye compoundrepresented by formula (1), (II), (III) or (IV):

wherein, m stands for 0, 1 or 2, n stands for 1 or 2, m units of R¹ andn units of R⁴ each independently represents a hydrogen atom, a C₁₋₄alkyl group or a halogen atom, m units of R² each independentlyrepresents a hydrogen atom, a C₁₋₄ alkyl group or an aryl group, withthe proviso that at m=2, two R²s, taken together with the adjacent═C—CH═C—, may form a carbocyclic structure or an oxygen-containingheterocyclic structure, n units of R³ each independently represents ahydrogen atom or a C₁₋₄ alkyl group, n units of R⁵ each independentlyrepresents a hydrogen atom or a C₁₋₄ alkyl group, or is bonded, via agroup —CO—O—, to a ring B⁵ to form a lactone ring, R⁶ represents ahydrogen atom or a C₁₋₄ alkyl group, A¹ represents the below-describedformula (1), (2) or (3), A² represents the below-described formula (4),A³ represents the below-described formula (5), (6), (7), (8) or (9), A⁴and Z¹ each independently represents the below-described formula (10),(11), (12), (13), (14), (15) or (16), Z² represents the below-describedformula (17), Z³ represents the below-described formula (18), (19), (20)or (21):

 wherein a broken line means the presence or absence of bonding, D¹represents an oxygen atom, a sulfur atom or a group NR²⁵, D² representsan oxygen atom, a sulfur atom, a group NR²⁶ or a group CR²⁷R²⁸, D³represents a nitrogen atom or a group CR²⁹, D⁴ represents an oxygenatom, a sulfur atom or a group NR³⁰, R⁷, R⁸, R⁹, R¹⁴ and R²⁵ eachindependently represents a C₁₋₆ alkyl group which may have asubstituent, R¹⁰, R¹¹, R¹³, R¹⁵, R¹⁶, R²¹, R²², R²⁷, R²⁸ and R²⁹ eachindependently represents a hydrogen atom or a C₁₋₆ alkyl group, R¹² andR²⁶ each independently represents a hydrogen atom or a C₁₋₆ alkyl groupwhich may have a substituent, R¹⁷ and R¹⁸ each independently representsa hydrogen atom, a C₁₋₆ alkyl group which may have a substituent or anaryl group which may have a substituent, or R¹⁷ and R¹⁸, taken togetherwith the adjacent nitrogen atom, form a nitrogen-containing heterocycleor one or both of R¹⁷ and R¹⁸ is (are) bonded to the ring B⁵ to form anitrogen-containing heterocycle, R¹⁹ and R²³ each independentlyrepresents an aryl group which may have a substituent, R²⁰ represents aC₁₋₆ alkyl group, R²⁴ and R³⁰ each independently represents a hydrogenatom, a C₁₋₆ alkyl group which may have a substituent, or an aryl groupwhich may have a substituent, Y¹ and Y² each independently represents anoxygen atom or a sulfur atom, rings B¹, B², B³ and B⁴ each independentlyhas a ring structure which may have, as a substituent, a halogen atom,an aryl group or a C₁₋₄ alkyl group or may further be cyclocondensedwith a benzene ring, B⁵ has a ring structure which may have, as asubstituent, a halogen atom, an aryl group or a C₁₋₄ alkyl group, may becondensed with a benzene ring, or may be bonded to R¹⁷ or R¹⁸ to have aring structure which may be cyclocondensed with a nitrogen-containingheterocycle, and X⁻ represents an anion, with the proviso that X⁻ doesnot exist when R⁷, R⁸, R⁹ and R²⁵ each has a sulfonium group as asubstituent, the first part having a pH ranging from 6-11 that isadjusted to within said range by an alkali agent; and second part,comprising an aqueous solution of an oxidizing agent.
 3. A hair dyecomposition, comprising: a three-part aqueous formulation comprising, ina first part, a direct dye compound represented by formula (1), (II),(III) or (IV):

wherein, m stands for 0, 1 or 2, n stands for 1 or 2, m units of R¹ andn units of R⁴ each independently represents a hydrogen atom, a C₁₋₄alkyl group or a halogen atom, m units of R² each independentlyrepresents a hydrogen atom, a C₁₋₄ alkyl group or an aryl group, withthe proviso that at m=2, two R²s, taken together with the adjacent═C—CH═C—, may form a carbocyclic structure or an oxygen-containingheterocyclic structure, n units of R³ each independently represents ahydrogen atom or a C₁₋₄ alkyl group, n units of R⁵ each independentlyrepresents a hydrogen atom or a C₁₋₄ alkyl group, or is bonded, via agroup —CO—O—, to a ring B⁵ to form a lactone ring, R⁶ represents ahydrogen atom or a C₁₋₄ alkyl group, A¹ represents the below-describedformula (1), (2) or (3), A² represents the below-described formula (4),A³ represents the below-described formula (5), (6), (7), (8) or (9), A⁴and Z¹ each independently represents the below-described formula (10),(11), (12), (13), (14), (15) or (16), Z² represents the below-describedformula (17), Z³ represents the below-described formula (18), (19), (20)or (21):

 wherein a broken line means the presence or absence of bonding, D¹represents an oxygen atom, a sulfur atom or a group NR²⁵, D² representsan oxygen atom, a sulfur atom, a group NR²⁶ or a group CR²⁷R²⁸, D³represents a nitrogen atom or a group CR²⁹, D⁴ represents an oxygenatom, a sulfur atom or a group NR³⁰, R⁷, R⁸, R⁹, R¹⁴ and R²⁵ eachindependently represents a C₁₋₆ alkyl group which may have asubstituent, R¹⁰, R¹¹, R¹³, R¹⁵, R¹⁶, R²¹, R²², R²⁷, R²⁸ and R²⁹ eachindependently represents a hydrogen atom or a C₁₋₆ alkyl group, R¹² andR²⁶ each independently represents a hydrogen atom or a C₁₋₆ alkyl groupwhich may have a substituent, R¹⁷ and R¹⁸ each independently representsa hydrogen atom, a C₁₋₆ alkyl group which may have a substituent or anaryl group which may have a substituent, or R¹⁷ and R¹⁸, taken togetherwith the adjacent nitrogen atom, form a nitrogen-containing heterocycleor one or both of R¹⁷ and R¹⁸ is (are) bonded to the ring B⁵ to form anitrogen-containing heterocycle, R¹⁹ and R²³ each independentlyrepresents an aryl group which may have a substituent, R²⁰ represents aC₁₋₆ alkyl group, R²⁴ and R³⁰ each independently represents a hydrogenatom, a C₁₋₆ alkyl group which may have a substituent, or an aryl groupwhich may have a substituent, Y¹ and Y² each independently represents anoxygen atom or a sulfur atom, rings B¹, B², B³ and B⁴ each independentlyhas a ring structure which may have, as a substituent, a halogen atom,an aryl group or a C₁₋₄ alkyl group or may further be cyclocondensedwith a benzene ring, B⁵ has a ring structure which may have, as asubstituent, a halogen atom, an aryl group or a C₁₋₄ alkyl group, may becondensed with a benzene ring, or may be bonded to R¹⁷ or R¹⁸ to have aring structure which may be cyclocondensed with a nitrogen-containingheterocycle, and X⁻ represents an anion, with the proviso that X⁻ doesnot exist when R⁷, R⁸, R⁹ and R²⁵ each has a sulfonium group as asubstituent, the first part having a pH ranging from 6-11 that isadjusted to within said range by an alkali agent; and a second part,comprising an aqueous solution of an oxidizing agent; and a third part,comprising a powdered oxidizing agent.
 4. The hair dye compositionaccording to claim 1, wherein the content of alkali in the compositionranges from 0.01 to 20 wt % of the formulation.
 5. The hair dyecomposition according to claim 2, wherein the oxidizing agent ishydrogen peroxide, a persulfate, a perborate, a percarbonate or abromate.
 6. The hair dye composition according to claim 2, wherein theoxidizing agent is present in the entire composition in an amount of 0.5to 10 wt %.
 7. The hair dye composition according to claim 2, whereinthe oxidizing agent is combined with a developer and a coupler in thesecond part of the composition, each present in an amount ranging from0.01 to 20 wt % of the entire composition.
 8. The hair dye compositionaccording to claim 3, wherein the oxidizing agent of the second part ishydrogen peroxide, a persulfate, a perborate, a percarbonate or abromate.
 9. The hair dye composition according to claim 3, wherein theoxidizing agent of the second part is present in the entire compositionin an amount of 0.5 to 10 wt %.
 10. The hair dye composition accordingto claim 3, wherein the oxidizing agent is combined with a developer anda coupler in the second part of the composition, each present in anamount ranging from 0.01 to 20 wt % of the entire composition.
 11. Thehair dye composition according to claim 3, wherein the third part of thecomposition contains a powdered persulfate oxidizing agent.
 12. A methodof dyeing hair, comprising: treating the hair with a one-part aqueousformulation containing a direct dye compound represented by formula (1),(II), (III) or (IV):

wherein, m stands for 0, 1 or 2, n stands for 1 or 2, m units of R¹ andn units of R⁴ each independently represents a hydrogen atom, a C₁₋₄alkyl group or a halogen atom, m units of R² each independentlyrepresents a hydrogen atom, a C₁₋₄ alkyl group or an aryl group, withthe proviso that at m=2, two R²s, taken together with the adjacent═C—CH═C—, may form a carbocyclic structure or an oxygen-containingheterocyclic structure, n units of R³ each independently represents ahydrogen atom or a C₁₋₄ alkyl group, n units of R⁵ each independentlyrepresents a hydrogen atom or a C₁₋₄ alkyl group, or is bonded, via agroup —CO—O—, to a ring B⁵ to form a lactone ring, R⁶ represents ahydrogen atom or a C₁₋₄ alkyl group, A¹ represents the below-describedformula (1), (2) or (3), A² represents the below-described formula (4),A³ represents the below-described formula (5), (6), (7), (8) or (9), A⁴and Z¹ each independently represents the below-described formula (10),(11), (12), (13), (14), (15) or (16), Z² represents the below-describedformula (17), Z³ represents the below-described formula (18), (19), (20)or (21):

 wherein a broken line means the presence or absence of bonding, D¹represents an oxygen atom, a sulfur atom or a group NR²⁵, D² representsan oxygen atom, a sulfur atom, a group NR²⁶ or a group CR²⁷R²⁸, D³represents a nitrogen atom or a group CR²⁹, D⁴ represents an oxygenatom, a sulfur atom or a group NR³⁰, R⁷, R⁸, R⁹, R¹⁴ and R²⁵ eachindependently represents a C₁₋₆ alkyl group which may have asubstituent, R¹⁰, R¹¹, R¹³, R¹⁵, R¹⁶, R²¹, R²², R²⁷, R²⁸ and R²⁹ eachindependently represents a hydrogen atom or a C₁₋₆ alkyl group, R¹² andR²⁶ each independently represents a hydrogen atom or a C₁₋₆ alkyl groupwhich may have a substituent, R¹⁷ and R¹⁸ each independently representsa hydrogen atom, a C₁₋₆ alkyl group which may have a substituent or anaryl group which may have a substituent, or R¹⁷ and R¹⁸, taken togetherwith the adjacent nitrogen atom, form a nitrogen-containing heterocycleor one or both of R¹⁷ and R¹⁸ is (are) bonded to the ring B⁵ to form anitrogen-containing heterocycle, R¹⁹ and R²³ each independentlyrepresents an aryl group which may have a substituent, R²⁰ represents aC₁₋₆ alkyl group, R²⁴ and R³⁰ each independently represents a hydrogenatom, a C₁₋₆ alkyl group which may have a substituent, or an aryl groupwhich may have a substituent, Y¹ and Y² each independently represents anoxygen atom or a sulfur atom, rings B¹, B², B³ and B⁴ each independentlyhas a ring structure which may have, as a substituent, a halogen atom,an aryl group or a C₁₋₄ alkyl group or may further be cyclocondensedwith a benzene ring, B⁵ has a ring structure which may have, as asubstituent, a halogen atom, an aryl group or a C₁₋₄ alkyl group, may becondensed with a benzene ring, or may be bonded to R¹⁷ or R¹⁸ to have aring structure which may be cyclocondensed with a nitrogen-containingheterocycle, and X⁻ represents an anion, with the proviso that X⁻ doesnot exist when R⁷, R⁸, R⁹ and R²⁵ each has a sulfonium group as asubstituent, the composition having a pH ranging from 6-11 that isadjusted to within said range by an alkali agent and containing at leastone cosmetic ingredient selected from the group consisting ofhydrocarbons, animal or vegetable fats and oils, fatty acids, organicsolvents, hair penetration promoters, cationic surfactants, natural orsynthetic polymers, alcohols, ethers, amphoteric surfactants, nonionicsurfactants, protein derivatives, amino acids, antiseptics, chelatingagents, stabilizing agents, antioxidants, plant extracts, crude drugextracts, vitamins, colorants, perfumes, aerosolizing agents and UVabsorbers.
 13. A method of dyeing hair, comprising: treating the hairwith a two-part aqueous formulation comprising, in a first part, adirect dye compound represented by formula (1), (II), (III) or (IV):

wherein, m stands for 0, 1 or 2, n stands for 1 or 2, m units of R¹ andn units of R⁴ each independently represents a hydrogen atom, a C₁₋₄alkyl group or a halogen atom, m units of R² each independentlyrepresents a hydrogen atom, a C₁₋₄ alkyl group or an aryl group, withthe proviso that at m=2, two R²s, taken together with the adjacent═C—CH═C—, may form a carbocyclic structure or an oxygen-containingheterocyclic structure, n units of R³ each independently represents ahydrogen atom or a C₁₋₄ alkyl group, n units of R⁵ each independentlyrepresents a hydrogen atom or a C₁₋₄ alkyl group, or is bonded, via agroup —CO—O—, to a ring B⁵ to form a lactone ring, R⁶ represents ahydrogen atom or a C₁₋₄ alkyl group, A¹ represents the below-describedformula (1), (2) or (3), A² represents the below-described formula (4),A³ represents the below-described formula (5), (6), (7), (8) or (9), A⁴and Z¹ each independently represents the below-described formula (10),(11), (12), (13), (14), (15) or (16), Z² represents the below-describedformula (17), Z³ represents the below-described formula (18), (19), (20)or (21):

 wherein a broken line means the presence or absence of bonding, D¹represents an oxygen atom, a sulfur atom or a group NR²⁵, D² representsan oxygen atom, a sulfur atom, a group NR²⁶ or a group CR²⁷R²⁸, D³represents a nitrogen atom or a group CR²⁹, D⁴ represents an oxygenatom, a sulfur atom or a group NR³⁰, R⁷, R⁸, R⁹, R¹⁴ and R²⁵ eachindependently represents a C₁₋₆ alkyl group which may have asubstituent, R¹⁰, R¹¹, R¹³, R¹⁵, R¹⁶, R²¹, R²², R²⁷, R²⁸ and R²⁹ eachindependently represents a hydrogen atom or a C₁₋₆ alkyl group, R¹² andR²⁶ each independently represents a hydrogen atom or a C₁₋₆ alkyl groupwhich may have a substituent, R¹⁷ and R¹⁸ each independently representsa hydrogen atom, a C₁₋₆ alkyl group which may have a substituent or anaryl group which may have a substituent, or R¹⁷ and R¹⁸, taken togetherwith the adjacent nitrogen atom, form a nitrogen-containing heterocycleor one or both of R¹⁷ and R¹⁸ is (are) bonded to the ring B⁵ to form anitrogen-containing heterocycle, R¹⁹ and R²³ each independentlyrepresents an aryl group which may have a substituent, R²⁰ represents aC₁₋₆ alkyl group, R²⁴ and R³⁰ each independently represents a hydrogenatom, a C₁₋₆ alkyl group which may have a substituent, or an aryl groupwhich may have a substituent, Y¹ and Y² each independently represents anoxygen atom or a sulfur atom, rings B¹, B², B³ and B⁴ each independentlyhas a ring structure which may have, as a substituent, a halogen atom,an aryl group or a C₁₋₄ alkyl group or may further be cyclocondensedwith a benzene ring, B⁵ has a ring structure which may have, as asubstituent, a halogen atom, an aryl group or a alkyl group, may becondensed with a benzene ring, or may be bonded to R¹⁷ or R¹⁸ to have aC₁₋₄ ring structure which may be cyclocondensed with anitrogen-containing heterocycle, and X⁻ represents an anion, with theproviso that X⁻ does not exist when R⁷, R⁸, R⁹ and R²⁵ each has asulfonium group as a substituent, the first part having a pH rangingfrom 6-11 that is adjusted to within said range by an alkali agent; anda second part, comprising an aqueous solution of an oxidizing agent. 14.A method of dyeing hair, comprising: treating the hair with a three-partaqueous formulation comprising, in a first part, a direct dye compoundrepresented by formula (1), (II), (III) or (IV):

wherein, m stands for 0, 1 or 2, n stands for 1 or 2, m units of R¹ andn units of R⁴ each independently represents a hydrogen atom, a C₁₋₄alkyl group or a halogen atom, m units of R² each independentlyrepresents a hydrogen atom, a C₁₋₄ alkyl group or an aryl group, withthe proviso that at m=2, two R²s, taken together with the adjacent═C—CH═C—, may form a carbocyclic structure or an oxygen-containingheterocyclic structure, n units of R³ each independently represents ahydrogen atom or a C₁₋₄ alkyl group, n units of R⁵ each independentlyrepresents a hydrogen atom or a C₁₋₄ alkyl group, or is bonded, via agroup —CO—O—, to a ring B⁵ to form a lactone ring, R⁶ represents ahydrogen atom or a C₁₋₄ alkyl group, A¹ represents the below-describedformula (1), (2) or (3), A² represents the below-described formula (4),A³ represents the below-described formula (5), (6), (7), (8) or (9), A⁴and Z¹ each independently represents the below-described formula (10),(11), (12), (13), (14), (15) or (16), Z² represents the below-describedformula (17), Z³ represents the below-described formula (18), (19), (20)or (21):

 wherein a broken line means the presence or absence of bonding, D¹represents an oxygen atom, a sulfur atom or a group NR²⁵, D² representsan oxygen atom, a sulfur atom, a group NR²⁶ or a group CR²⁷R²⁸, D³represents a nitrogen atom or a group CR²⁹, D⁴ represents an oxygenatom, a sulfur atom or a group NR³⁰, R⁷, R⁸, R⁹, R¹⁴ and R²⁵ eachindependently represents a C₁₋₆ alkyl group which may have asubstituent, R¹⁰, R¹¹, R¹³, R¹⁵, R¹⁶, R²¹, R²², R²⁷, R²⁸ and R²⁹ eachindependently represents a hydrogen atom or a C₁₋₆ alkyl group, R¹² andR²⁶ each independently represents a hydrogen atom or a C₁₋₆ alkyl groupwhich may have a substituent, R¹⁷ and R¹⁸ each independently representsa hydrogen atom, a C₁₋₆ alkyl group which may have a substituent or anaryl group which may have a substituent, or R¹⁷ and R¹⁸, taken togetherwith the adjacent nitrogen atom, form a nitrogen-containing heterocycleor one or both of R¹⁷ and R¹⁸ is (are) bonded to the ring B⁵ to form anitrogen-containing heterocycle, R¹⁹ and R²³ each independentlyrepresents an aryl group which may have a substituent, R²⁰ represents aC₁₋₆ alkyl group, R²⁴ and R³⁰ each independently represents a hydrogenatom, a C₁₋₆ alkyl group which may have a substituent, or an aryl groupwhich may have a substituent, Y¹ and Y² each independently represents anoxygen atom or a sulfur atom, rings B¹, B², B³ and B⁴ each independentlyhas a ring structure which may have, as a substituent, a halogen atom,an aryl group or a C₁₋₄ alkyl group or may further be cyclocondensedwith a benzene ring, B⁵ has a ring structure which may have, as asubstituent, a halogen atom, an aryl group or a C₁₋₄ alkyl group, may becondensed with a benzene ring, or may be bonded to R¹⁷ or R¹⁸ to have aring structure which may be cyclocondensed with a nitrogen-containingheterocycle, and X⁻ represents an anion, with the proviso that X⁻ doesnot exist when R⁷, R⁸, R⁹ and R²⁵ each has a sulfonium group as asubstituent, the first part having a pH ranging from 6-11 that isadjusted to within said range by an alkali agent; and a second part,comprising an aqueous solution of an oxidizing agent; and a third part,comprising a powdered oxidizing agent.